US8674049B1 - Silicone containing aromatic film forming polymers - Google Patents

Silicone containing aromatic film forming polymers Download PDF

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Publication number
US8674049B1
US8674049B1 US13/507,580 US201213507580A US8674049B1 US 8674049 B1 US8674049 B1 US 8674049B1 US 201213507580 A US201213507580 A US 201213507580A US 8674049 B1 US8674049 B1 US 8674049B1
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yes
silicone
difunctional
film forming
following structure
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Thomas G. O'Lenick
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SurfaTech Corp
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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/892—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a hydroxy group, e.g. dimethiconol
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q3/00—Manicure or pedicure preparations
    • A61Q3/02—Nail coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
    • C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences

Definitions

  • the present invention is directed to polymers that are useful in nail polish applications.
  • the specific film forming polyester polymers that are liquids in solvents like butyl acetate, form a uniform film upon application when in a solvent (most commonly butyl acetate), evaporates under atmospheric conditions and at the same time can be removed easily and thoroughly by application of a solvent like acetone.
  • the polymers have as critical part of the polymer a silicone portion which provides flexibility, tear resistance and superior aesthetics.
  • the films and the colors and other ingredients present in the film need to apply in a uniform film and remain functional and cosmetically acceptable on the nail in terms of scuffing, breaking when struck, pliable over the period of time during which they are on the nails.
  • the film that forms in the above process must possess specific cosmetic benefits, including ability to disperse colors, be scuff resistant, resistant to cracking when struck, remain pliable and cosmetically appealing.
  • One of the major properties the consumers finds appealing is gloss. Gloss in a film of this type is generally difficult to attain by adding ingredients. The inclusion of an aromatic components directly into the film. This is generally accomplished by adding into the reaction mixture, trimellitic anhydride. This aromatic anhydride alters the refractive index of the film providing gloss.
  • U.S. Pat. No. 4,301,046 issued in November 1981 to Mitchell Schlossman, a pioneer in the field, entitled Universal nail polish using polyester resin disclosed a nail polish is made from 92% to 96% ingredients including a film former, colorant, plasticizer and solvent; and 4% to 8% polyester resin made from 2,2,4-trimethyl-1,3-pentanediol, isophthalic acid-85, and trimellitic anhydride, having an acid value of 75-85 and a viscosity of 125-175 centipoise.
  • the polyester is made from 50.932% 2,2,4 trimethyl-1,3-pentanediol, 27.579% isophthalic acid-85, 0.186% dibutyl tin oxide catalyst and 21.303 trimellitic anhydride, having an acid value of 80 and a viscosity of 150 centipoise.
  • silicone as a reactant in the polymer mixture results in many highly desirable attributes and makes a more cosmetically appealing film. Firstly, polymers containing silicone result in better more uniform films when applied to the nail. Not wanting to be bound by a single theory, this appears to be the result of a lowering of the surface tension of the film when applied. Secondly, polymers containing silicone are more flexible when applied to the nails, this makes them less likely to break upon a physical insult, and less likely to undergo a cut damage when sharp items are encountered by the film. Finally, polymers containing silicone are more easily removed with acetone, in part because they are easily wet out by the solvent in silicone is present, a result related to the low surface tension of silicone containing films, compared to non silicone containing films of comparable composition.
  • the present invention is drawn to a polymer that contains silicone within the polymer backbone. This results in new heretofore unattainable properties in nail polish.
  • the present invention is directed to a process for treating nails, which comprises contacting the nails with the polymers of the present invention additionally containing colors.
  • the present invention is directed to a film-forming polymer which is synthesized by the esterification reaction of (1) a difunctional organic polyol; (2) a difunctional silicone polyol a difunctional; (3) an organic acid (4) a difunctional silicone and (5) trimellitic anhydride.
  • film forming is meant a polymer that is liquid at ambient temperatures, at 70-80% by weight polymer in 20-30% volatile solvent, typically acetone or butyl acetate but forms a uniform film when the solvent evaporates.
  • the liquid solution at obtained by addition of solvent ambient temperature is transformed when the solvent evaporates into a uniform film that adheres to the nail, and is removable using acetone in a subsequent step.
  • the present invention is directed to a film-forming polymer which is synthesized by the esterification reaction of
  • a is an integer ranging from 1 to 20;
  • a difunctional organic acid selected from the group consisting of; HO—C(O)—(CH 2 ) b —C(O)—OH and
  • b is an integer ranging from 1 to 10;
  • c is an integer ranging from 1 to 20;
  • the present invention is also directed to a process for applying color to the nail or skin which comprises of a film-forming polymer which is made by the reaction of;
  • a is an integer ranging from 1 to 20;
  • a difunctional organic acid selected from the group consisting of; HO—C(O)—(CH 2 ) b —C(O)—OH and
  • b is an integer ranging from 1 to 10;
  • c is an integer ranging from 1 to 20;
  • the proper selection raw materials used to make the polymers of the present inventions determine the properties of the film that result.
  • the polymers of the present invention make films, which are of interest in making nail polish.
  • the polymer In order to make polymers suitable for the application, the polymer must be a liquid when present in butyl acetate, dry to a film upon evaporation, then become soluble again in solvents like acetone. It is this solubility which allows for application and removal, but as importantly, the polymer needs to have attributes the consumer finds desirable like gloss, resistance to scuff and flexibility.
  • the applicant has surprisingly found that incorporating silicone containing reactants in the polymers of the present invention provides great scuff residence, great spread ability when compared to the polymer with the silicone absent, wear properties when applied to the nail and the ability to flow on the nail are all improved.
  • trimellitic anhydride in the polymer increases the refractive index of the compounds of the present invention providing much desired gloss. Furthermore, the rigidity of the trimellitic repeat unit improves the durability of the film. It is well known when rigid units, in a polymer backbone, increase the glass transition temperature (T g ).
  • the compounds of the present invention are polyesters and as such avoid the undesirable properties of being made from vinyl reactive monomers, which need to be removed to vanishingly low concentrations to avoid potentially toxic products present in the polymers of the present invention.
  • the film-forming polymer which is made by the reaction of;
  • the film-forming polymer additionally contains a solvent selected from the group consisting of butyl acetate and acetone.
  • a is 1.
  • a is 1.
  • a is 5.
  • a is 10.
  • a is 20.
  • b is 4.
  • c is 1.
  • c is 1.
  • c is 5.
  • c is 10.
  • Neopentyl glycol is an item of commerce available from a variety of sources including BASF. It conforms to the following structure:
  • 2,2,4-trimethyl-1,3-pentanediol is an item of commerce available from a variety of sources including Sigma Aldrich. It conforms to the following structure:
  • the CAS number is 144-19-4.
  • Difunctional silicone polymers are items of commerce commercially available from Siltech LLC of Lawrenceville Ga. They conform to the following structure;
  • c is an integer ranging from 1 to 20;
  • a is an integer ranging from 1 to 20;
  • Difunctional organic acids are items of commerce commercially available from BASF. They conform to the following structure; HO—C(O)—(CH 2 ) b —C(O)—OH
  • Isophthalic acid is an item of commerce commercially available from a number of suppliers including Tianjin Ruihui chemicals import & export co., ltd.
  • Difunctional silicone polymers are items of commerce commercially available from Siltech LLC of Lawrenceville Ga. They conform to the following structure;
  • c is an integer ranging from 1 to 20;
  • Trimellitic anhydride is an item of commerce commercially available from Sigma Aldrich. It conforms the following structure;
  • Butyl acetate is an item of commerce commercially available from a variety of sources including Sciencelab.com, Inc. It conforms to the following structure;
  • Acetone is an item of commerce commercially available from a variety of sources including Sigma Aldrich.
  • color is meant colors allowed by the Food and Drug Administration (FDA)
  • the compounds of the present invention are prepared by an esterification reaction.
  • the products as prepared have 25% butyl acetate added to make a liquid solution at ambient temperature. When the solvent evaporates, a uniform film is left which adheres to the nail, and is removable using acetone.
  • the polymers of the present invention can be tailored for particular functionality as requested by the consumer. Firstly, as the concentration of aromatic compound (trimellitic anhydride and isophthalic acid), the refractive index of the film increases and the gloss increases. Matte films result when the concentration falls below 20% by weight. Secondly, as the concentration of the silicone difunctional silicone glycol increases in the polymer, the plasticity of the dry down film increases. Thirdly, if the concentration of the silicone polymer containing carboxyl groups is increases, the dry time of the film increases. This is because a C11 fatty group in incorporated into the molecule. Fourthly, it the organic acid concentration is increased, the film becomes more brittle. Brittle nail polishes crack and are not acceptable to the consumer.
  • aromatic compound trimellitic anhydride and isophthalic acid
  • the films provided by the polymers of the present invention are by nature transient films that is the materials are low viscosity liquids when the butyl acetate is present. They spread easily on the nail. Incorporating silicone into the polymer enhances this spreadbility, as the resulting surface tension of the polymer in butyl acetate decreases from 32 dynes/cm to 25 dynes/cm. Once the film forms, it needs to efficiently disperse the color and once again silicone in the molecule helps in this regard. When the nail polish has outlived the consumer's interest in it, the film must be effectively removed with solvents like acetone. If the film is too heavily crosslinked, the film deposited will be very difficult to remove.
  • the perfect nail polish is a balancing act. Balancing the ease of application, spreadability, color deposition, gloss, flexibility and ease of removal. Silicone in the molecule results in an ability to enhance the various properties demanded by the consumer, and adds an overall unexpected improvement in many of the properties when made in accordance with the teachings of the present invention.

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Abstract

The present invention is directed to polymers that are useful in nail polish applications. The specific film forming polyester polymers that are liquids in solvents like butyl acetate, form a uniform film upon application when in a solvent (most commonly butyl acetate), evaporates under atmospheric conditions and at the same time can be removed easily and thoroughly by application of a solvent like acetone. The polymers of the present invention having a silicone portion contained therein provide improved flexibility, tear resistance and superior aesthetics.

Description

RELATED APPLICATIONS
None
GOVERNMENT SPONSORSHIP
None
FIELD OF THE INVENTION
The present invention is directed to polymers that are useful in nail polish applications. The specific film forming polyester polymers that are liquids in solvents like butyl acetate, form a uniform film upon application when in a solvent (most commonly butyl acetate), evaporates under atmospheric conditions and at the same time can be removed easily and thoroughly by application of a solvent like acetone. The polymers have as critical part of the polymer a silicone portion which provides flexibility, tear resistance and superior aesthetics.
BACKGROUND OF THE INVENTION
The cosmetic placing of color onto the nail of humans has loon been a desirable and part of the cosmetic world. The physical and chemical demands of color so applied are dramatic. Specifically, the following considerations need to be addressed (1) how to apply color in a film that is easy to applied in a process at ambient conditions; (2) how to obtain a cosmetically acceptable film, in terms of color clarity, and gloss; (3) how to maintain the film and the desirable properties that the consumer demands over a period of time that the film remains on the skin; (4) how to assure resistance to environmental insults the nails are subjected to during the lifetime of the polish; (5) and how to thoroughly remove the film efficiently and thoroughly when the consumer desires the removal, and finally how to do this in a cost effective way.
It must be clearly understood that the process of decorative application of color to the nails by a consumer is fundamentally different from painting a wall or other permanent film applications. Unlike the application of paint, nail colors need to be removable thoroughly and effectively at the whim of the consumer. The color is in many regards a fashion item and can change quite often in a short period of time.
This ability to be easily removed at any time, coupled with the need to be accomplished by the consumer in a home environment, places limitations upon the type of process that can be used, in terms of application technique (limited to brush application) at ambient conditions and using no special equipment.
In addition to need for facile application and removal as desired by the consumer, the films and the colors and other ingredients present in the film need to apply in a uniform film and remain functional and cosmetically acceptable on the nail in terms of scuffing, breaking when struck, pliable over the period of time during which they are on the nails. The film that forms in the above process must possess specific cosmetic benefits, including ability to disperse colors, be scuff resistant, resistant to cracking when struck, remain pliable and cosmetically appealing. One of the major properties the consumers finds appealing is gloss. Gloss in a film of this type is generally difficult to attain by adding ingredients. The inclusion of an aromatic components directly into the film. This is generally accomplished by adding into the reaction mixture, trimellitic anhydride. This aromatic anhydride alters the refractive index of the film providing gloss.
U.S. Pat. No. 4,301,046 issued in November 1981 to Mitchell Schlossman, a pioneer in the field, entitled Universal nail polish using polyester resin disclosed a nail polish is made from 92% to 96% ingredients including a film former, colorant, plasticizer and solvent; and 4% to 8% polyester resin made from 2,2,4-trimethyl-1,3-pentanediol, isophthalic acid-85, and trimellitic anhydride, having an acid value of 75-85 and a viscosity of 125-175 centipoise. In another example, the polyester is made from 50.932% 2,2,4 trimethyl-1,3-pentanediol, 27.579% isophthalic acid-85, 0.186% dibutyl tin oxide catalyst and 21.303 trimellitic anhydride, having an acid value of 80 and a viscosity of 150 centipoise.
The inclusion of silicone as a reactant in the polymer mixture results in many highly desirable attributes and makes a more cosmetically appealing film. Firstly, polymers containing silicone result in better more uniform films when applied to the nail. Not wanting to be bound by a single theory, this appears to be the result of a lowering of the surface tension of the film when applied. Secondly, polymers containing silicone are more flexible when applied to the nails, this makes them less likely to break upon a physical insult, and less likely to undergo a cut damage when sharp items are encountered by the film. Finally, polymers containing silicone are more easily removed with acetone, in part because they are easily wet out by the solvent in silicone is present, a result related to the low surface tension of silicone containing films, compared to non silicone containing films of comparable composition.
THE INVENTION Objective of the Invention
The present invention is drawn to a polymer that contains silicone within the polymer backbone. This results in new heretofore unattainable properties in nail polish.
In addition, the present invention is directed to a process for treating nails, which comprises contacting the nails with the polymers of the present invention additionally containing colors. Other Objectives of the invention will become clear as one reads the specification of the invention.
All patents referenced herein are incorporated herein by reference to the extent allowed. Unless specifically stated elsewhere all temperatures are in degrees C., and all % given are % by weight.
SUMMARY OF THE INVENTION
The present invention is directed to a film-forming polymer which is synthesized by the esterification reaction of (1) a difunctional organic polyol; (2) a difunctional silicone polyol a difunctional; (3) an organic acid (4) a difunctional silicone and (5) trimellitic anhydride. By film forming is meant a polymer that is liquid at ambient temperatures, at 70-80% by weight polymer in 20-30% volatile solvent, typically acetone or butyl acetate but forms a uniform film when the solvent evaporates. The liquid solution at obtained by addition of solvent ambient temperature, is transformed when the solvent evaporates into a uniform film that adheres to the nail, and is removable using acetone in a subsequent step.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a film-forming polymer which is synthesized by the esterification reaction of
(a) a difunctional organic polyol selected from the group consisting of
Figure US08674049-20140318-C00001
and mixtures thereof;
(b) a difunctional silicone polyol which conforms the following structure;
Figure US08674049-20140318-C00002
wherein;
a is an integer ranging from 1 to 20;
(c) a difunctional organic acid selected from the group consisting of;
HO—C(O)—(CH2)b—C(O)—OH and
Figure US08674049-20140318-C00003
mixtures thereof;
wherein;
b is an integer ranging from 1 to 10;
(d) a difunctional silicone ester which conforms the following structure;
Figure US08674049-20140318-C00004
wherein;
c is an integer ranging from 1 to 20;
and
(e) trimellitic anhydride conforming the following structure;
Figure US08674049-20140318-C00005
The present invention is also directed to a process for applying color to the nail or skin which comprises of a film-forming polymer which is made by the reaction of;
(a) a difunctional organic polyol selected from the group consisting of
Figure US08674049-20140318-C00006
(b) a difunctional silicone polyol which conforms the following structure;
Figure US08674049-20140318-C00007
wherein;
a is an integer ranging from 1 to 20;
(c) a difunctional organic acid selected from the group consisting of;
HO—C(O)—(CH2)b—C(O)—OH and
Figure US08674049-20140318-C00008
wherein;
b is an integer ranging from 1 to 10;
(d) a difunctional silicone acid which conforms the following structure;
Figure US08674049-20140318-C00009
wherein;
c is an integer ranging from 1 to 20;
and
(e) trimellitic anhydride conforming the following structure;
Figure US08674049-20140318-C00010
additionally containing color and solvent.
The proper selection raw materials used to make the polymers of the present inventions determine the properties of the film that result. The polymers of the present invention make films, which are of interest in making nail polish.
In order to make polymers suitable for the application, the polymer must be a liquid when present in butyl acetate, dry to a film upon evaporation, then become soluble again in solvents like acetone. It is this solubility which allows for application and removal, but as importantly, the polymer needs to have attributes the consumer finds desirable like gloss, resistance to scuff and flexibility. The applicant has surprisingly found that incorporating silicone containing reactants in the polymers of the present invention provides great scuff residence, great spread ability when compared to the polymer with the silicone absent, wear properties when applied to the nail and the ability to flow on the nail are all improved.
The inclusion of the trimellitic anhydride in the polymer increases the refractive index of the compounds of the present invention providing much desired gloss. Furthermore, the rigidity of the trimellitic repeat unit improves the durability of the film. It is well known when rigid units, in a polymer backbone, increase the glass transition temperature (Tg).
The compounds of the present invention are polyesters and as such avoid the undesirable properties of being made from vinyl reactive monomers, which need to be removed to vanishingly low concentrations to avoid potentially toxic products present in the polymers of the present invention.
PREFERRED EMBODIMENTS
In a preferred embodiment the film-forming polymer which is made by the reaction of;
    • (a) between 10 and 63% by weight of a difunctional organic polyol selected from the group consisting of;
Figure US08674049-20140318-C00011
    • (b) a difunctional organic acid selected from the group consisting of;
      HO—C(O)—(CH2)b—C(O)—OH and
Figure US08674049-20140318-C00012
wherein;
    • b is an integer ranging from 1 to 10;
    • (c) between 2 and 10% by weight of a difunctional silicone polyol which conforms the following structure;
Figure US08674049-20140318-C00013
    • wherein c is an integer ranging from 1 to 20;
      and
    • (d) 30-60% by weight of trimellitic anhydride conforming the following structure;
Figure US08674049-20140318-C00014
In a preferred embodiment process the film-forming polymer additionally contains a solvent selected from the group consisting of butyl acetate and acetone.
In a preferred embodiment a is 1.
In a preferred embodiment a is 1.
In a preferred embodiment a is 5.
In a preferred embodiment a is 10.
In a preferred embodiment a is 20.
In a preferred embodiment b is 4.
In a preferred embodiment c is 1.
In a preferred embodiment c is 1.
In a preferred embodiment c is 5.
In a preferred embodiment c is 10.
EXAMPLES Difunctional Organic Polyol Example 1 Neopentyl Glycol
Neopentyl glycol is an item of commerce available from a variety of sources including BASF. It conforms to the following structure:
Figure US08674049-20140318-C00015
It has a CAS number of 126-30-7.
Example 2 2,2,4-trimethyl-1,3-pentanediol
2 2,2,4-trimethyl-1,3-pentanediol is an item of commerce available from a variety of sources including Sigma Aldrich. It conforms to the following structure:
Figure US08674049-20140318-C00016
The CAS number is 144-19-4.
Difunctional Silicone Polyol Examples 3-6
Difunctional silicone polymers are items of commerce commercially available from Siltech LLC of Lawrenceville Ga. They conform to the following structure;
Figure US08674049-20140318-C00017
wherein
c is an integer ranging from 1 to 20;
a is an integer ranging from 1 to 20;
Example A value
3 1
4 5
5 10
6 20
Difunctional Organic Acids Examples 7-11
Difunctional organic acids are items of commerce commercially available from BASF. They conform to the following structure;
HO—C(O)—(CH2)b—C(O)—OH
    • wherein;
    • b is an integer ranging from 1 to 10.
Molecular Weight
Example B (g/mol)
7 5 237
8 8 367
9 15 676
10 23 1027
11 25 1116
Example 12 Isophthalic Acid
Isophthalic acid is an item of commerce commercially available from a number of suppliers including Tianjin Ruihui chemicals import & export co., ltd.
It conforms to the following structure:
Figure US08674049-20140318-C00018
It has a CAS number of 121-91-5.
Difunctional Silicone Acid Examples 13-16
Difunctional silicone polymers are items of commerce commercially available from Siltech LLC of Lawrenceville Ga. They conform to the following structure;
Figure US08674049-20140318-C00019
wherein;
c is an integer ranging from 1 to 20;
Example c value
13 1
14 5
15 10
16 20
Example 17 Trimellitic Anhydride
Trimellitic anhydride is an item of commerce commercially available from Sigma Aldrich. It conforms the following structure;
Figure US08674049-20140318-C00020
CAS no. 552-30-7
EINECS 209-008-0
Example 18 Butyl Acetate
Butyl acetate is an item of commerce commercially available from a variety of sources including Sciencelab.com, Inc. It conforms to the following structure;
Figure US08674049-20140318-C00021
It has a CAS number of 123-86-4.
Example 19 Acetone
Acetone is an item of commerce commercially available from a variety of sources including Sigma Aldrich.
Figure US08674049-20140318-C00022
It has a CAS number of 67-64-1.
By color is meant colors allowed by the Food and Drug Administration (FDA)
Color Additives Permitted for Use in Cosmetics: Table
Apr. 30, 2008; Updated Jun. 20, 2008 and Feb. 22, 2010
The tables below are provided as a supplement to the information in the Summary of Color Additives Listed for Use in the United States in Food, Drugs, Cosmetics, and Medical Devices. They are intended for quick reference to help in determining which color additives may be used in different types of cosmetics, as provided for in Title 21 of the Code of Federal Regulations (CFR), Subpart C of Part 73 (Listing of Color Additives Exempt from Certification), Subpart C of Part 74 (Listing of Color Additives Subject to Certification), and Subparts C and D of Part 82 (Listing of Certified Provisionally Listed Colors and Specifications). For additional information on the permitted use, specifications, and restrictions that apply to each color additive, please refer to the appropriate listing regulation, using the links provided in the tables. For more information on the use of color additives in cosmetics in general, please see Color Additives and Cosmetics.
Color Additives that are Exempt from Certification and Permitted for Use in Cosmetics
(21 CFR Part 73 Subpart C - Cosmetics)
Generally
Eye (Includes External 21 CFR
Color Additive Area Lipsticks) Use Section
Aluminum powder Yes No Yes 73.2645
Annatto Yes Yes Yes 73.2030
Bismuth citrate No No Subject to 73.2110
limitations
Bismuth oxychloride Yes Yes Yes 73.2162
Bronze powder Yes Yes Yes 73.2646
Caramel Yes Yes Yes 73.2085
Carmine Yes Yes Yes 73.2087
β-Carotene Yes Yes Yes 73.2095
Chromium hydroxide Yes No Yes 73.2326
green
Chromium oxide greens Yes No Yes 73.2327
Copper powder Yes Yes Yes 73.2647
Dihydroxyacetone No No Subject to 73.2150
limitations
Disodium EDTA-copper No No Subject to 73.2120
limitations
Ferric ammonium Yes No Yes 73.2298
ferrocyanide
Ferric ferrocyanide Yes No Yes 73.2299
Guaiazulene No No Yes 73.2180
Guanine Yes Yes Yes 73.2329
Henna No No Subject to 73.2190
limitations
Iron oxides Yes Yes Yes 73.2250
Lead acetate No No Subject to
limitations
Luminescent zinc sulfide No No Subject to 73.2995
limitations
Manganese violet Yes Yes Yes 73.2775
Mica Yes Yes Yes 73.2496
Potassium sodium copper No No Subject to 73.2125
chlorophyllin limitations
(chlorophyllin-copper
complex)
Pyrophyllite No No Yes 73.2400
Silver No No Subject to 73.2500
limitations
Titanium dioxide Yes Yes Yes 73.2575
Ultramarines Yes No Yes 73.2725
Zinc oxide Yes Yes Yes 73.2991
Additives That Are Subject to Certification and
Permitted for Use in Cosmetics*
Includes Straight Colors and Lakes
(21 CFR Part 74 Subpart - Cosmetics, and 21
CFR Part 82 Subpart C - Drugs and Cosmetics and
Subpart D - Externally Applied Drugs and Cosmetics)
Generally
(Includes 21 CFR
Color Additive Eye Area** Lipsticks) External Use Section
D&C Black Subject to Subject to Subject to 74.2052
No. 2 Limitations Limitations Limitations
D&C Black Subject to No Subject to 74.2053
No. 3 Limitations Limitations
FD&C Blue Yes, also Al Yes Yes 74.2101
No. 1 lake
D&C Blue No. 4 No No Yes 74.2104
D&C Brown No No Yes 74.2151
No. 1
FD&C Green No Yes Yes 74.2203
No. 3
D&C Green No. 5 Yes Yes Yes 74.2205
D&C Green No. 6 No No Yes 74.2206
D&C Green No. 8 No No Subject to 74.2208
Limitations
D&C Orange No No Yes 74.2254
No. 4
D&C Orange No Subject to Yes 74.2255
No. 5 Limitations
D&C Orange No No Yes 74.2260
No. 10
D&C Orange No No Yes 74.2261
No. 11
FD&C Red No. 4 No No Yes 74.2304
D&C Red No. 6 No Yes Yes 74.2306
D&C Red No. 7 No Yes Yes 74.2307
D&C Red No. 17 No No Yes 74.2317
D&C Red No. 21 No Yes Yes 74.2321
D&C Red No. 22 No Yes Yes 74.2322
D&C Red No. 27 No Yes Yes 74.2327
D&C Red No. 28 No Yes Yes 74.2328
D&C Red No. 30 No Yes Yes 74.2330
D&C Red No. 31 No No Yes 74.2331
D&C Red No. 33 No Subject to Yes 74.2333
Limitations
D&C Red No. 34 No No Yes 74.2334
D&C Red No. 36 No Subject to Yes 74.2336
Limitations
FD&C Red No. 40 Yes, Yes Yes 74.2340
D&C Violet No No Yes 74.2602
No. 2
Ext. D&C Violet No No Yes 74.2602a
No. 2
FD&C Yellow Yes, also Al Yes Yes 74.2705
No. 5 lake
FD&C Yellow No Yes Yes 74.2706
No. 6
D&C Yellow No No Yes 74.2707
No. 7
Ext. D&C Yellow No No Yes 74.2707a
No. 7
D&C Yellow No No Yes 74.2708
No. 8
D&C Yellow No Yes Yes 74.2710
No. 10
D&C Yellow No No Yes 74.2711
No. 11
*Includes straight colors and lakes
**Excludes lakes except where noted. Only aluminum lakes on alumina are permitted for designated lakes.
Preparation of the Polymers of the Present Invention
The compounds of the present invention are prepared by an esterification reaction.
General Procedure
To a suitable reaction flask, able to heat contents to 200° C. with good agitation and the ability to distill off water is added the specified number of grams of the specified difunctional glycol Examples 1-2); next add the specified number of grams of the specified difunctional silicone glycol Examples (3-6); next add the specified number of grams of the specified organic acid Examples (7-12); next add the specified number of grams of the specified trimellitic anhydride (Examples 17); finally add 0.2 grams of stannous oxylate. Heat to 170-190° C. and react for 4-6 hours, monitoring acid value. When acid value approaches 80 mg KOH/gm, cool the reaction mass. Once cool add 300 grams of butyl acetate.
Difunctional
Difunctional Silicone Organic Difunctional Trimetillic
Glycol Glycol Acid Silicone Anhydride
Examples Ex g Ex g Ex g Ex g Ex G
20 1 294 3 229 7 42 13 29 17 407
21 2 419 4 94 12 25 14 95 17 367
22 1 275 5 138 9 120 15 129 17 405
23 1 333 3 54 11 184 13 27 17 402
24 2 419 4 94 12 25 14 95 17 367
25 1 305 5 150 7 36 15 141 17 368
26 2 369 6 230 11 30 16 35 17 337
27 1 382 3 63 12 32 13 32 17 491
28 2 379 4 85 9 118 14 118 17 332
29 1 295 5 148 8 55 15 139 17 363
30 2 438 3 51 12 26 14 100 17 415
31 1 389 3 63 7 24 13 24 17 415
32 2 473 3 55 7 28 13 28 17 415
33 1 211 3 25 7 12 13 12 17 415
34 2 252 4 30 12 16 15 16 17 415
The products as prepared have 25% butyl acetate added to make a liquid solution at ambient temperature. When the solvent evaporates, a uniform film is left which adheres to the nail, and is removable using acetone.
APPLICATIONS EXAMPLES
The polymers of the present invention can be tailored for particular functionality as requested by the consumer. Firstly, as the concentration of aromatic compound (trimellitic anhydride and isophthalic acid), the refractive index of the film increases and the gloss increases. Matte films result when the concentration falls below 20% by weight. Secondly, as the concentration of the silicone difunctional silicone glycol increases in the polymer, the plasticity of the dry down film increases. Thirdly, if the concentration of the silicone polymer containing carboxyl groups is increases, the dry time of the film increases. This is because a C11 fatty group in incorporated into the molecule. Fourthly, it the organic acid concentration is increased, the film becomes more brittle. Brittle nail polishes crack and are not acceptable to the consumer.
It must be clearly understood that the films provided by the polymers of the present invention are by nature transient films that is the materials are low viscosity liquids when the butyl acetate is present. They spread easily on the nail. Incorporating silicone into the polymer enhances this spreadbility, as the resulting surface tension of the polymer in butyl acetate decreases from 32 dynes/cm to 25 dynes/cm. Once the film forms, it needs to efficiently disperse the color and once again silicone in the molecule helps in this regard. When the nail polish has outlived the consumer's interest in it, the film must be effectively removed with solvents like acetone. If the film is too heavily crosslinked, the film deposited will be very difficult to remove.
In short, the perfect nail polish is a balancing act. Balancing the ease of application, spreadability, color deposition, gloss, flexibility and ease of removal. Silicone in the molecule results in an ability to enhance the various properties demanded by the consumer, and adds an overall unexpected improvement in many of the properties when made in accordance with the teachings of the present invention.
While the illustrative embodiments of the invention have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions set forth hereinabove but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention, including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains.

Claims (17)

The invention claimed is:
1. A silicone containing film-forming polymer which is made by the esterification reaction of;
(a) a difunctional organic polyol selected from the group consisting of
Figure US08674049-20140318-C00023
and mixtures thereof;
(b) a difunctional silicone polyol which conforms the following structure;
Figure US08674049-20140318-C00024
wherein;
a is an integer ranging from 1 to 20;
(c) a difunctional organic acid selected from the group consisting of;

HO—C(O)—(CH2)b—C(O)—OH and
Figure US08674049-20140318-C00025
and mixtures thereof;
wherein;
b is an integer ranging from 1 to 10;
(d) a difunctional silicone acid which conforms the following structure;
Figure US08674049-20140318-C00026
wherein;
c is an integer ranging from 1 to 20;
and
(e) trimellitic anhydride conforming the following structure;
Figure US08674049-20140318-C00027
2. A silicone film forming polymer of claim 1 wherein a is 1.
3. A silicone film forming polymer of claim 1 wherein a is 5.
4. A silicone film forming polymer of claim 1 wherein a is 10.
5. A silicone film forming polymer of claim 1 wherein a is 20.
6. A silicone film forming polymer of claim 1 wherein b is 4.
7. A silicone film forming polymer of claim 1 wherein c is 1.
8. A silicone film forming polymer of claim 1 wherein c is 5.
9. A silicone film forming polymer of claim 1 wherein c is 10.
10. A process for applying color to the nail or skin which comprises addition of a film-forming silicone polymer which is made by the esterification reaction of;
(a) a difunctional organic polyol selected from the group consisting of
Figure US08674049-20140318-C00028
(b) a difunctional silicone polyol which conforms the following structure;
Figure US08674049-20140318-C00029
wherein;
a is an integer ranging from 1 to 20;
(c) a difunctional organic acid selected from the group consisting of;

HO—C(O)—(CH2)b—C(O)—OH and
Figure US08674049-20140318-C00030
wherein;
b is an integer ranging from 1 to 10;
(d) a difunctional silicone acid which conforms the following structure;
Figure US08674049-20140318-C00031
wherein;
c is an integer ranging from 1 to 20;
and
(e) trimellitic anhydride conforming the following structure;
Figure US08674049-20140318-C00032
additionally containing pigment and solvent.
11. The process of claim 10 wherein a is 1.
12. The process of claim 10 wherein a is 10.
13. The process of claim 10 wherein a is 20.
14. The process of claim 10 wherein b is 4.
15. The process of claim 10 wherein c is 1.
16. The process of claim 10 wherein c is 5.
17. The process of claim 10 wherein c is 10.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4301046A (en) * 1980-01-10 1981-11-17 Tevco Inc. Universal nail polish using polyester resin
US5210133A (en) * 1992-06-15 1993-05-11 Siltech Inc. Silicone polyester polymers as delivery systems
US5538717A (en) * 1993-10-15 1996-07-23 L'oreal Aqueous nail polish containing as film-forming substance particles of polyester-polyurethane which are anionic in dispersion
US7524919B2 (en) * 2006-09-29 2009-04-28 Sabic Innovative Plastics Ip B.V. Polycarbonate-polysiloxane copolymers, method of making, and articles formed therefrom

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4301046A (en) * 1980-01-10 1981-11-17 Tevco Inc. Universal nail polish using polyester resin
US5210133A (en) * 1992-06-15 1993-05-11 Siltech Inc. Silicone polyester polymers as delivery systems
US5538717A (en) * 1993-10-15 1996-07-23 L'oreal Aqueous nail polish containing as film-forming substance particles of polyester-polyurethane which are anionic in dispersion
US7524919B2 (en) * 2006-09-29 2009-04-28 Sabic Innovative Plastics Ip B.V. Polycarbonate-polysiloxane copolymers, method of making, and articles formed therefrom

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